Aminoalkylene sulfonic acid containing phenols

ABSTRACT

THIS INVENTION RELATES TO NOVEL IMMOBILE REDUCING AGENTS OF THE P-AMIOPHENOL TYPE WHICH MAY BE DEFINED AS ZWITTERIONIC (INNER) SALTS OF P-AMINOPHENOLS CONTAINING AN ANCHORING OR IMMOBILIZING MOIETY.

United States Paten O1 fice 3,597,474 Patented Aug. 3, 1971 3,597,474AMHNOALKYLENE SULIFONIIC ACID CONTAlNlNG PHENOLS Stanley M. Bloom,Waban, and Paul S. Huylfer, Lynnfield, Mass, assignors to PolaroidCorporation, Cambridge, Mass.

No Drawing. Original application July 24, 1967, Ser. No. 655,309, nowPatent No. 3,459,548, dated Aug. 5, 1969. Divided and this applicationSept. 16, 1968, Ser. No, 810,403

lint. Cl. C07c 143/52, 143/64 US. Cl. 260-507R 8 Claims ABSTRACT OF THEDISCLOSURE This invention relates to novel immobile reducing agents ofthe p-aminophenol type which may be defined as zwitterionic (inner)salts of p-aminophenols containing an anchoring or immobilizing moiety,

This application is a division of copending U.S. Ser. No. 655,309 filedJuly 24, 1967 and now US. Pat. 3,459,- 548 issued Aug. 5, 1969.

BACKGROUND OF THE INVENTION The copending application of Stanley M.Bloom and Howard G. Rogers, Ser. No. 655,440 filed concurrently (Pat.No. 3,443,940) describes and claims certain photographic procedures forforming positive color transfer images wherein a photosensitive elementcontaining at least one light-sensitive silver halide emulsion and anassociated layer of color-providing material is exposed and thendeveloped with an aqueous alkaline processing composition including asilver halide solvent and a silver halide developing agent. As afunction of development, an imagewise distribution of soluble silvercomplex is formed, and this imagewise distribution migrates to theassociated color-providing material where it is reduced and thecolor-providing material is in turn liberated for transfer to asuperposed stratum to impart thereto a positive color transfer image.

In the practice of this photographic procedure, care must be taken toavoid a redox reaction between oxidized developing agent formed as afunction of development and the color-providing material, since thisredox reaction interferes with the system upon which selective transferof color-providing material to the superposed stratum to form thedesired image is predicated.

One system for obviating this redox reaction is to incorporate in thephotosensitive element a reducing agent or scavenger for the oxidizeddeveloper which will reduce the latter before it has had opportunity toreact with the color-providing material. The scavenger should ideallyprovide an immobile reaction product so that it will be unable tomigrate to the superposed stratum where it might adversely affect thecolor and/or stability of the desired color image.

SUMMARY The present invention is directed to a novel class of reducingagents which are of particular use in the aforementioned photographicprocesses and in procedures generally where it is desired that thereducing agent be immobile or non-migratory. The reducing agents of thisinvention are also silver halide developing agents.

The novel reducing agents of this invention contain an immobilizing oranchoring substituent which effectively precludes unwanted migration ofthe compound from its layer in the photosensitive element, whichmigration may adversely affect image formation by the previouslydescribed photographic system.

As was mentioned previously, the present invention is directed to novelreducing agents.

A primary object of this invention, therefore, is to provide a novelclass of reducing agents.

Another object is to provide a novel class of reducing agents orscavengers of the foregoing description.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the product possessing the features,properties and the relation of components which are exemplified in thefollowing detailed disclosure, and the scope of the application of whichwill be indicated in the claims.

For a fuller understanding of the nature and objects of the invention,reference should be had to the following detailed description.

The novel reducing agents of this invention may be represented by thefollowing formula:

Ann-i) B (n) A represents an anchoring or immobilizing substituentrendering the compound non-diffusible, e.g., higher alkyl, e.g., of atleast eight carbon atoms, such as octyl, decyl, dodecyl, stearyl, oleyl,etc. linked directly to the aromatic nucleus or linked indirectlythereto through an appropriate linking group, e.g., -CONH;-alkylene-CONH:

etc., an aromatic ring, e.g., of the benzene or naphthalene series whichrings may be either bonded to a single carbon atom of the aromaticnucleus or fused thereto, i.e., bonded to a pair of adjacent carbonatoms, or A may be a plurality of short chain radicals which togetherprovide the anchoring moiety, each of the short chain radicals beinglinked directly or indirectly to a different carbon atom on the benzenenucleus;

B is carboxy, alkoxy, alkyl, chloro or an amide substituent; n is apositive integer from 1 to 3;

The alkylene moiety contains at least two carbon atoms, e.g., from 2 to18 carbon atoms, and preferably from 2 to 4 carbon atoms, and may be astraight or a branched chain; and

m is a positive integer from 1 to 2, provided that where the alkylenemoiety alone or together with said B substituent provides an anchoringor immobilizing substituent 121 may be 1, but when it does not, then 111must be 2.

The compounds of this invention may be prepared by the followingsequence of steps:

Where the alkylene moiety contains from 2-4 carbon atoms, the desiredcompound may also be obtained by employing as step II, the followingreaction:

B (011 Product The particular reaction conditions, e.g., time,temperature, pressure, etc. are not critical and will be readilyapparent to those skilled in the art.

As examples of novel reducing agents contemplated by this invention,mention may be made of the following:

Because of the anchoring moiety rendering the compound non-diffusiblefrom the layer in which it is present, migration of the compound to thelayer containing the color-providing material is effectively precluded,thereby in turn precluding unwanted competition between scavenger andcolor-providing material for reduction of the soluble silver complexformed as a function of development.

The inner salt or zwitterionic form of the p-aminophenol-type compoundaffords significant advantages over p-aminophenols in general in thatthe latter are not stable in the photosensitive element and, uponcontact, will desensitize the emulsion; whereas the inner salt form ofthis invention is highly stable and does not so desensitize theemulsion.

The following examples show by way of illustration and not by way oflimitation the practice of this invention.

Example 1 38.6 g. of 6-nitrodehydrocoumarin was dissolved in 400.0 cc.of methyl Cellosolve. 28.4 g. of n-octylamine were added and the mixturewas heated on a steam bath for 30 minutes and then cooled. Filtrationyielded 40.2 g. of a light yellow compound, M.P. l79-180 C. of theformula:

40.2 g. of the last-named nitro compound 15.8 g. of

propane sultone 200.0 cc. of methanol and 5% palladium/barium sulfatewere placed in a pressure vessel. Hydrogen was introduced and thereaction mixture was shaken for four hours after theoretical hydrogenuptake. 100.0 cc. more of methanol were then added and the mixture wasboiled and then filtered. Cooling of the filtrate yielded 23 g. of thepure white compound of Formula 1, M.P. 196197 C.

Example 2 11.0 g. of 6-nitrodehydrocoumarin was dissolved in 100.0 cc.of methyl Cellosolve. 12.0 g. of n-dodecylamine were then added. (Thereaction was exothermic and a yellow solid separated out.) The mixturewas heated until a clear solution was obtained and then cooled to give14.0 g. of light yellow crystals, M.P. 168-170" C., an amide of theformula:

l lo:

27.5 g. of the above amide (prepared in the foregoing manner) and 9.28g. of propane sultone (10% excess) were placed in a pressure vessel.200.0 cc. of methanol and 5% Pd/BaSO were added and the mixture was thenhydrogenated at 40 p.s.i. The reaction mixture was shaken for four hoursafter theoretical hydrogen uptake. An additional 100.0 cc. of methanolwere then added and the mixture was heated. to boiling, filtered andcooled. After cooling, 11.65 g. of the compound of Formula 2 wereobtained, a white solid, M.P. 207-208 C. An additional 2 g. of thiscompound were obtained after concentration of the filtrate.

Example 3 A photosensitive element of the type disclosed in theaforementioned copending application Ser. No. 655,440 was prepared bycoating on a cellulose acetate support a gelatin layer containing acolloidal silver silver-preeipitating agent and non-ditfusiblecolor-providing compound of the formula:

to provide a calculated coverage of 136 mgm. per square foot of each ofthe color-providing compound and the silver precipitating agent;applying over this a layer containing a calculated coverage of 136 mgm.per square foot of gelatin and the same amount of a compound of Formula1; and finally coating on a light-sensitive gelatino silver iodobromideemulsion. This element was then exposed and developed by spreadingbetween the thus exposed element and a superposed dyeable sheet materialat a gap of .0026 a processing composition containing the followingproportions of ingredients:

G. Hydroxyethyl cellulose 3.9 Sodium hydroxide 5.0 Sodium thiosulfate2.0 Sodium sulfite 2.0

Metol 1.6

Water-l00.0 cc.

After an imbibition time of about two minutes, the elements wereseparated to reveal a positive dye transfer image.

Example 4 A similar photosensitive element containing no scavenger wasexposed and developed in the manner described in Example 3. When theelements were separated following imbibition, dye had transferred inboth exposed and unxposed areas so that no image formation wasobservable.

Example 5 A photosensitive element was prepared as in Example 3, exceptthat the compound of Formula 1 was included in the silver halideemulsion layer at a calculated coverage of 68 mgm. per square foot. Thisphotosensitive element was exposed and developed in the manner describedin Example 3 with a developing composition containing the followingproportions of ingredients:

G. Hydroxyethyl cellulose 3.9 Sodium hydroxide 5.0 Sodium thiosulfate L1.0

Water100.0 cc.

The gap employed was .0016. After two minutes the elements wereseparated to reveal a positive dye image.

From the procedure described in Example 5, it will be observed that thecompounds of this invention may be employed as silver halide developingevents. While they are primarily intended for use in the processesdescribed above, and illustrative Example 5 so indicates theirusefulness in such processes, it will be apparent that they may find useas silver halide developing agents in other photographic processes,e.g., processes wherein the use of an immobile or relatively immobiledeveloper is desirable. Ac-

cordingly, it is to be expressly understood that the photographicutilization of the compounds of this invention is not restricted toproducts and processes such as were described in Examples 3-5.

By way of recapitulation the compounds of this invention areparticularly useful in the photographic systems described and claimed inthe aforementioned Ser. No. 655,440 wherein a photosensitive elementincluding at least one light-sensitive silver halide emulsion havingassociated therewith a non-diffusible color-providing material which iscapable of providing an oxidation product which can auto-reactintramolecularly to effect ringclosure and to eliminate thecolor-providing moiety of said material for transfer is exposed and thendeveloped with an aqueous alkaline processing composition including asilver halide solvent and a silver halide developing agent the oxidationproduct of which is reducible by a redox reaction with thecolor-providing material; and imagewise distribution of soluble silvercomplex is formed in terms of unexposed areas of the emulsion; thenon-diifusible colorproviding material is contacted with the imagewisedistribution of soluble silver complex where, in the presence ofsilver-precipitating nuclei, the complex is reduced and as a functionthereof an imagewise distribution of oxidized color-providing materialis formed; the oxidized material is allowed to auto-reactintramolecularly to eliminate the color-providing moiety to provide animagewise distribution of diffusible color-providing moiety in terms ofunexposed areas of the emulsion; and this imagewise distribution ofcolor-providing moiety is transferred, at least in part, by imbibition,to a superposed stratum to impart thereto a positive color transferimage. In one procedure described in this copending application, ascavenger for oxidized developer is positioned in a layer in thephotosensitive element between the emulsion layer and the layer ofcolor-providing material, so that oxidized developer formed as afunction of development is reduced before it can migrate to the layer ofcolor-providing material and there undergo an undesired redox reactionwith the colorproviding material.

Since the novel compounds of this invention are effectively immobile intheir reduced form, they cannot migrate to the layer of color-providingmaterial where they would compete with the color-providing material asreducing agents for the soluble silver complex, which competing would bedeterimental to proper image formation.

Since certain changes may be made in the above product and processwithout departing from the scope of the invention herein involved it isintended that all matter contained in the above description shall beinterpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A compound of the formula NH -alkylene-SOa wherein, A is an anchoringsubstituent rendering the compound non dilfusible, said substituentbeing a higher alkyl of from 818 carbon atoms linked directly to thearomatic nucleus or linked indirectly to said nucleus through a linkingmoiety chosen from the group consisting of or A is the moiety which,when bonded to the 2,3 nuclear carbon atoms of said pictured benzenenucleus, can provide a naphthalene nucleus.

8 B is a substituent chosen from the group consisting of 6. CH OCH andCOOH; n is O or 1 and alkylene con- OH tains from 212 carbon atoms. I

2. A compound as defined in claim 1 wherein said alkyl- E JL ene moietycontains from 2 to 4 carbon atoms. 5 C N 9 NHzcH c1-I -CH2-s03 1 0 H n10 CHz-CHz-CNGaH 7-I1 0H I? HO 0 O CIIT-CHzON-C8H17 NH2-CI{2CH2CH2-S 0315 4. 1 11Iz-oII2--0H -so3 OH I i 20 OH @OHzCH CNO H -n I Q i 9NHPoHPcHr-om-sm 19 NH CHzCH CH SOa References Cited OH UNITED STATESPATENTS H 2,319,078 5/1943 McNally et a1. 260409 H -oo H N DANIEL D.HORWITZ,P1-1mary Examiner U.S. Cl. X.R.

